Sulphonic acids and process of preparing them



Patented Apr. 13, 1943 FFICE 'sULPnoNro ACIDS AND rnocnss or raamama mmLudwig .Orthner and Werner Langbein, Frank i'ort-on-the-Main, Germany;vested in the Alien Property Custodian No Drawing. Application August 3.1940, Serial No. 351,153. In Germany July 13, 1939 Claims. (Cl. 260-513)The present invention relates to sulphonic acids and to a process ofpreparing them. It is an object of the invention to prepare sulphonic;

acids from beta-halogenether compounds and alkali sulphites, the newcompounds having capillary active properties and being suitable asadjuvants in the textile industry, for instance as wetting, dispersingand washing agents.

We have found that sulphon-ic acids are obtained by reacting alkalisulphites with betahalogen-ethers prepared by condensing alkylene oxideswith a. member of the group consisting of halogen-methyl-ethers derivedfrom: aliphatic and carbocyclic compounds containing an ali phaticradical with at least four carbon atoms and further containing at leastone hydroxyl group, and halogenmethylamides derived from aliphatic andcarbocyclic carboxylic and sulphonic acids containing an aliphaticradical with at least four carbon atoms. The products obtained may bedesignated by the following general formula wherein R stands for amember of the group consisting of aliphatic and carbocyclic radicalscontaining an aliphatic radical with at least four carbon atoms, and Xstands for a member of the group consisting of oxygen, carboxylic acidamide and sulphonic acid amide.

As aliphatic or carbocyclic compounds containing at least one aliphaticradical with four carbon atoms and further containing at least -0nealcoholic hydroxyl group, there may be and oils, in the synthesis ofmethanol or in the hydrogenation of the products obtained by theoxidation of parafilne, for lnstance the alcoholic mixtures obtained bythe hydrogenation of palm oil or coconut oil. The carbon skeleton of thecompounds containing at least one alcoholic hydroxyl group maybeinterrupted by hetero atoms or hetero atom groups. As such compoundsthere may be named, for instance: isooctylphenylmonoglycolether andp-dodecyl-N- dihydroxyethylaniline. I I

The halogenmethyl-ethers may be obtained in the usual manner from thecompounds named, for instance by the action oi'vformaldehyde andhydrochloric acid, if necessary in the presence of an indifferentsolvent or diluent.

In order to obtain halogenmethyl-a'mides, there may be used as startingmaterials the amides of the following acids: butyric acid, caproic acid,caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid,linolic acid, further the amides of the carboxylic acids obtained by thesaponification of whale oil or by the oxidation of parafines. Moreoverthere may be used sulphamides, especially those obtained'by thesimultaneous action of sulphur dioxide and chlorine upon paraifinehydrocarbons and the subsequent reaction with ammonia. 'Moreover thereare suitable for the process of the present invention the amides fromalkylated aromatic, hydroaromatic or araliphatic carboxylic or sulphonicacids. I

From the amides the halogenmethyl-amides may be obtained, for instanceby'the action of formaldehyde and hydrochloric acid, if necessary in thepresence of an indifferent solvent or diluent.

The beta-halogenethers obtainable by reacting the halogen-methyl-ethersor -amides with a suitable alpha, beta-alkylenoxide, for instanceethylene oxide, propylene oxide, butylene dioxide, glycide, if necessaryat a raised temperature and 'under pressure, are transformed into ethersulphonic acids by the action of alkali sulphite, for instance byheating them to about 160-170 C. in an aqueous or aqueous-alcoholicsolution.

' The process of the present invention makes use of easily obtainablealcohols or alcoholic mixtures or of amides or mixtures of amides,products with valualble capillary active properties being obtained in asimple manner. The ethersulphonic acids so obtained constitute in theform of their salts in some cases viscous masses, in other cases .whiteto yellowish, water-soluble powders. The products have an excellent stability towards the agents which cause the hardness of water and a goodwetting, foaming, emulsifying and washing power. Some of the productsmay also be used as leveling, through-dyeing and softening agents Aswashing agents the products serve for cleansing household articles andtextile materials, especially wool, cotton, silk, artificial silk, aswell as for hygienic pur- The products may be used either alone or inadmixture with each other or with other capillary active substances,such as soap and other adiuvants of the textile industry, with colloidalsubstances, as for instance mucilage, glue, water- 2 Somme cellulosederivatives, starch, bentonite,

- saponine or the like, as well as in admixture with C., while stirring,until the solution is saturated.

After the separation of the aqueous layer the product is dried by meansof calcium chloride and filtered, whereupon the methylene chloride isseparated by distillation. The octylchloromethylether obtained is thendistilled under reduced pressure.

178.5 parts of octylchloromethylether are heated with 60 parts ofethylene oxide for 6 hours in a closed vessel at 160 C. to 170 C. Theethylene oxide in excess is then separated. By the absorption of 1 moi.of ethylene oxide the octylmethyl-ether-beta-chloroethylether has beenformed. 7

222.5 parts of the above ether are heated for 10 hours, while stirring,at 150-160 C. with a solution of 170 parts of sodium sulphite in 400parts of water and 800 parts of methanol. After cooling the product isfiltered with suction and recrystallized from methanol.

(2) 234.5 parts of dodecyl-chloromethyl-ether V are heated for 6 hoursat 160-170 C. with 60 parts of ethylene oxide, the solution being workedup in the manner indicated in Example 1. 278.5 parts of thedodecyl-methylether-betachloroethylether obtained having the formulaC12H25-OCHPO- H:-CH:-Cl are heated for 10 hours at 150-160 C. with asolution of 210 parts of potassium sulphite in 400 parts of water and800 parts of methanol. After coolin the product is filtered with suctionand recrystallized from methanol,

(3) 360.5 parts of oleylchloromethylether are heated for 6 hours at160-170 C. with 60 parts of ethylene oxide. 316.5 parts of theoleylmethylether-beta-chloroethylether obtained are heated for 10 hours,while stirring, at 150-160 C. with a solution of 170 parts ofsodiumsulphite in 400 parts of water and 800 parts of methanol. The product isredissolved from methanol.

(4) 262.5 parts of the chloromethylether from the mixture of alcoholsobtainable by the reduction of palm oil, are heated for 8 hours atISO-170 C. with 60 parts of ethylene oxide. 306.5 parts of thebeta-chloroethylether obtained are heated for 10 hours, while stirring,at 150-160 C.

with a solution 1'70 parts of sodium sulphite in 400 parts of water and800 parts of methanol. The product obtained may be redissolved frommethanol. I

(5) 178.5 parts of the chloromethylether derived from a mixture ofalcohols containing 7 to 9 carbon atoms, obtainable by the oxidation ofparamne, are heated for 6 hours at 160-170 C. with 60 parts of ethyleneoxide. 222.5 parts of the beta-chloroethylether obtained are heated for10 hours, while stirring, at 150-160 C. with a solution of 1'70 parts ofsodium sulphite in 400 parts of water and 800 parts of methanol. Theproduct obtained may be redissolved from methanol.

(6) 250 parts of octyiphenylmonoglycolether are dissolved in twice thequantity of methylene chloride. 45 parts of para-formaldehyde are thenadded and hydrochloric acid gas is introduced at 0-5 C., while stirring,until the solution is saturated. After the separation of the aqueouslayer, the solution is dried by means of calcium chloride. Afterfiltering, the methylene chloride is separated by distillation. 298.5parts of octylphenyl monoglycoletherchloromethylether are heated for 6hours at 160-170 C. with 60 parts of ethylene oxide. 342.5 partsof theoctylphenylmonoglycolether methylether-beta-chloroethylether obtainedare heated for 10 hours, while stirring, at l50-l60 C. with a solutionof 170 parts of sodium sulphite in 400 parts of water and 800 parts ofmethanol. The product obtained is purified by redissolving it frommethanol.

(7) 375.5 parts of stearic acid beta-chloroethoxymethylamide are heatedfor 10 hours. whilestirring, at 150-160 C. with a solution of 170 partsof sodium sulphite in 400 parts of water and 800 parts of methanol.After cooling, the sodium salt of the sulphonic acid having the formulais filtered with suction and recrystallized from methanol. Instead ofsodium sulphite there may be used potassium sulphite. The initialmaterial is obtained as follows:

283 parts of stearic acid amide are dissolved in twice the quantity ofmethylene chloride. 45 parts of paraformaldehyde and parts ofpulverulent calcium chloride are then added, hydrochloric acid gas beingintroduced at 0 C.-5 C., while stirring, until the solution issaturated. The solution is filtered with suction and rapidly dried bymeans of further calcium chloride. After filtering the methylenechloride is separated by distillation: the stearlc acidchloromethylamide remains in form of a fatty mass.

331.5 parts of stearic acid chloromethylamide are heated for 6 hours atISO-170 C. in a closed vessel with 60 parts of ethylene oxide, whereuponthe ethylene oxide in excess is separated. With absorption of l mol ofethylene oxide the stearic acid beta-chloroethoxymethylamide has beenformed.

roethoxymethylamide obtainable in the manner fdescribed below, areheated for 10 hours at C. with a solution of 210 parts of potassiumsulphite in 400 parts of water and 800 parts of methanol. After cooling,the product is filtered with suction and redissolved from methanol.

The initial material is obtained as follows:

By treating parafilne hydrocarbons having a boiling point of 220-320 C.,with equimolecular amounts of sulphur dioxide and chlorine, a mixture ofaliphatic sulphochlorides is obtained. By reacting this mixture withammonia, a mixture of aliphatic sulphamides having an average carbonchain of 14 atoms is obtained. By proceeding in the manner indicated inExample v7, a mixture of aliphatic sulphochloromethylamides is finallyobtained.

326.5 parts of this mixture are heated 1on6 hours at 160-170 C. with 60parts of ethylene oxide, the product being worked up as indicated in e7. (0) 312 parts of dodecylcyclohexylmonoglycolether are transformedinto the chloromethylether by the action of 45 parts of'paraiformaldehyde and hydrochloric acid. 'By' reacting thischloromethylether with ethylene oxide, thedodecylcyclohexylmonoglycolether methylether beta chloroethylether isobtained, which is then transformed into the corresponding sulphonate'by means of sodium sulphite in an aqueous methanol solution. Thesulphonate obtained may be redissolved from methanol.

(.10) 263 parts of octylphenoxyacetic acid amide are dissolved in twicethe amount of methylene chloride. 45 parts of paraformaldehyde and 90parts oi. anhydrous sodium sulphate are then added, hydrochloric acidgas being introduced at C.- 0., until the solution is saturated. Afterfiltering, the methylene chloride is separated by distillation.

311.5 parts of the octylphenoxyacetic acid chloromethylamide are heatedat 160-170 C. with parts of ethylene oxide, whereupon the ethylene I tilwe claim: 0 g 1. The process which comprises reacting ahalogemnethyl-etherot an aliphatic compound containing an aliphaticradical of at least 4 carbon atoms and at least 1 hydroxyl group with analv kyienoxideand reacting the resulting compound with an alkalisulphite.

2. The process which comprises reacting chlormethyi-ether o1 dodecylalcohol with ethylene oxids and reacting the resultingbeta-chlor-ethylether with an alkali sulphite to replace the betachlorgroup :by a sulphonic acid group.

3. The process as defined in claim 1 wherein the reaction with thealkali sulphite is effected at a temperature ranging from to C.

4. ,As new compounds the sulphonic' acids of the general formula whereinR stands for an aliphatic radical with at least iour carbon atoms, and Xstands for oxygen.

' 5'. The compound 01' the formula cmms-mcna-o-cns-cni-soan LUDWIG oamnaWERNER moans.

